Hydrazone‐Linked Donor‐Acceptor Covalent Organic Polymer as a Heterogeneous Photocatalyst for C−S Bond Formation

In the realm of solar energy utilization, there is a growing focus on designing and implementing effective photocatalytic systems, for the conversion of solar energy into valuable chemical fuels. The potential of Covalent Organic Polymers (COPs) as photocatalysts for visible‐light‐driven organic transformation has been widely investigated, positioning them as promising candidates in this field. In the design of COPs, introducing a donor‐acceptor arrangement facilitates the transfer of electrons from the donor to the acceptor, creating a charge transfer complex and leading to enhanced conductivity and improved charge separation. Here we present a novel hydrazone‐linked covalent organic polymer ETBC‐PyHz containing TPE donor and pyridine acceptor. Utilizing this, an efficient method has been developed for an oxidative cross‐coupling reaction involving C−S bond formation. This process involves arylhydrazines and arenethiols, and results in the production of unsymmetrical diaryl sulfides via the formation of aryl and thioarene radicals. This conversion holds significant importance because the byproducts produced during the process are nitrogen and water, making it environmentally benign. We present a novel hydrazone‐linked donor‐acceptor covalent organic polymer ETBC‐PyHz, as an efficient photocatalyst for an oxidative cross‐coupling reaction involving C−S bond formation. This environment‐friendly method does not require a metal‐based catalyst and does not generate side products.